CN1708527A - Polyurethane compounds and articles prepared therefrom - Google Patents
Polyurethane compounds and articles prepared therefrom Download PDFInfo
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- CN1708527A CN1708527A CNA2003801025171A CN200380102517A CN1708527A CN 1708527 A CN1708527 A CN 1708527A CN A2003801025171 A CNA2003801025171 A CN A2003801025171A CN 200380102517 A CN200380102517 A CN 200380102517A CN 1708527 A CN1708527 A CN 1708527A
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- isocyanatomethyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2120/00—Compositions for reaction injection moulding processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
This invention relates to polyurethane compounds, for example, elastomers, which are the reaction product of a cycloaliphatic diisocyanate, a polyol and a chain extender. The cycloaliphatic diisocyanate comprises (i) trans-l,4bis(isocyanatomethyl)cyclohexane or (ii) an isomeric mixture of two or more of cis1,3-bis(isocyanatomethyl)cyclohexane, trans- 1,3-bis(isocyanatomethyl)cyclohexane, cis-1,4-bis(isocyanatomethyl)cyclohexane and trans- l,4bis(isocyanatomethyl)cyclohexane, provided the isomeric mixture comprises at least 5 weight percent of said trans- l,4-bis(isocyanatomethyl)cyclohexane. This invention also relates to shaped and molded articles prepared from said polyurethane compounds.
Description
The present invention relates to based on some alicyclic diisocyanate, for example 1,3-and 1, the urethanes of 4 pairs of (isocyanatomethyl (isocyanatomethyl)) hexanaphthenes, elastomerics for example, this alicyclic diisocyanate and one or more oligomeric polyols and one or more short-chain diols and/or amine copolymer the invention still further relates to from the shaping and the moulded parts of this urethanes preparation.
Polyurethane elastomer is known article of commerce, it be characterized as good wear resistance, toughness, intensity, extensibility, low temperature flexibility, chemicals-resistant and oil-proofness and other chemistry and physicals.These machineries and each level of chemical factor depend on the component of forming any particular polyurethane or the proper property of constructing block materials.
The component that is used to form urethanes comprises three kinds of essential structure blocks: polyvalent alcohol, polyisocyanates and chainextender.Selection and ratio by these structure blocks in conjunction with preparation technology and required urethane type, can prepare the multiple urethane with wide kind performance.But but the type of polyurethane elastomer comprises thermoplastic elastomer, thermo-setting elastomer millable gums, liquid curtain coating material and micro-pore elastomer.
Polyurethane product, particularly elastomerics are used for some application of product coating or outside surface therein, may need this layer of polyurethane to keep transparent.According to the chemical property of polyisocyanates, have less commercially available aliphatic polyisocyanate, this aliphatic polyisocyanate when combining with commercially available polyvalent alcohol and chainextender, the good quality urethane that obtains having not flavescence He have good weatherability properties.
Therefore need have urethane that improves machinery and/or chemical property and/or the urethane of being made by following polyisocyanates: this polyisocyanates has the ratio of the isocyanate functionality of lower volatility and/or increase to the polyisocyanates molecular weight.Very required urethane is based on those of following component: this component generation has good mechanical and chemical property, not flavescence characteristic, the good photosensitiveness of anti-sun the, good weatherability properties, transparent polymkeric substance also can adopt environmental friendliness and cost efficient manner to reach these performances.
Find with known, commercial polyisocyanates is compared with the urethane of chainextender prepared in reaction with identical polyvalent alcohol, from alicyclic diisocyanate, it is anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the urethanes of the isomer mixture preparation of two (isocyanatomethyl) hexanaphthenes of 4-has excellent strength characteristics, resistance to elevated temperatures, good low temperature flexibility, the excellent in resistance marquis's characteristic that comprises anti-sunlight performance and not flavescence performance, condition is that isomer mixture comprises at least 5 these anti-form-1s of weight %, and two (isocyanatomethyl) hexanaphthenes of 4-are with the various ratios of these components or structure block, this alicyclic diisocyanate and polyester, polylactone, polyethers, polyolefine or polycarbonate polyol and saturated or unsaturated, linearity or the reaction of branching chainextender.The present invention also comprises from the shaping and the moulded parts of novel polyurethane preparation of the present invention.
The present invention relates to a kind of urethane, this urethane comprises alicyclic diisocyanate, the reaction product of polyvalent alcohol and chainextender, wherein this alicyclic diisocyanate comprises (i) anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or (ii) two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, condition is that this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.
The present invention also relates to comprise alicyclic diisocyanate, the polyurethane precursor composition of polyvalent alcohol and chainextender, wherein this alicyclic diisocyanate comprises (i) anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or (ii) two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, condition is that this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.
The invention further relates to the composition of the isomer mixture that comprises following material: cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-, wherein this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.
The present invention also further relates to the composition of the isomer mixture that comprises following material: cis-1, two (amino methyl) hexanaphthenes of 3-, anti-form-1, two (amino methyl) hexanaphthenes of 3-, cis-1, two (amino methyl) hexanaphthenes of 4-and anti-form-1, two (amino methyl) hexanaphthenes of 4-, wherein this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (amino methyl) hexanaphthenes of 4-.
Urethane of the present invention can be thermoplasticity or heat cured and can be by the following mode crosslinkable that becomes: by introducing unsaturated part or change component proportions in chainextender or polyvalent alcohol, make remaining functionality keep (but as in millable gums) after polyurethane preparation.Urethane can prepare by mixing all compositions substantially simultaneously in " single step (one-shot) " technology, or can in " prepolymer technology ", prepare by progressively adding each composition, the described herein inessential composition of this method exists and carries out down or do not add inessential composition described herein.Urethane formation is reflected in the body or carries out in solution, adds or do not add appropriate catalyst, and this catalyzer promotes the reaction of isocyanic ester and hydroxyl or other functionality.Urethane of the present invention can be prepared into soft and have high elongation rate, has low elongation firmly, and is weather-proof, and colour stable and not flavescence.
Polyurethane elastomer of the present invention can be thought the block or the chain segment copolymer of (AB) n type, this multipolymer comprises soft chain segment, the A part of molecule, and hard segment, the B part of molecule, as at J.Applied Polymer Sci. (applied polymer science periodical), 19, described in the 2503-2513 (1975).Weight % (wt%) hard segment is to add the part by weight of chainextender gram number divided by the urethane gross weight with the polyisocyanates gram number of chainextender reaction.
Be used for alicyclic diisocyanate of the present invention and comprise (i) anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or (ii) two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, condition is that this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.When using mixture, preferred anti-form-1, at least 10% of 4-isomer comprises mixture.For elastomeric production, when using mixture, preferred anti-form-1, at least 20% of 4-isomer comprises mixture.Preferred alicyclic diisocyanate is represented to IV by following structural formula I:
Anti-form-1, two (the isocyanatomethyl)-hexanaphthenes of 3-
Structural formula I
Cis-1, two (the isocyanatomethyl)-hexanaphthenes of 3-
Structural formula II
Anti-form-1, two (the isocyanatomethyl)-hexanaphthenes of 4-
Structural formula II I
Cis-1, two (the isocyanatomethyl)-hexanaphthenes of 4-
Structural formula IV
These alicyclic diisocyanates can be used for mixture; for example make: the Diels-Alder of divinyl and vinyl cyanide (Diels-Alder) reaction from following mode; hydroformylation subsequently; reduction amination is to form amine then; it is cis-1; 3-hexanaphthene-two (amino methyl); anti-form-1; 3-hexanaphthene two (amino methyl); cis-1; 4-hexanaphthene-two (amino methyl) and anti-form-1,4-hexanaphthene two (amino methyls), subsequently with phosgene reaction to form the alicyclic diisocyanate mixture.The preparation of hexanaphthene-two (amino methyl) is described in U.S. patent 6,252,121.Polyurethane composition of the present invention comprises 10 to 50 weight %, preferred 15 to 410 weight %, more preferably 15 to 35 isocyanic ester.
Being used for polyvalent alcohol of the present invention is the compound that comprises two or more isocyanate-reactive groups.The representative substances of suitable polyvalent alcohol is general known and is described in open source literature such as High Polymers, Vol.XVI; " polyurethanes, chemistry and technoogy (urethane, chemistry and technology) ", Saunders and Frisch, Interscience Publishers, New York, Vol.I, pp.32-42,44-54 (1962) and Vol II.Pp.5-6,198-199 (1964); OrganicPolymer Chemistry (organic polymer chemistry), K.J.Saunders, Chapman and Hall, London, pp.323-325 (1973); With developments in polyurethanes (progress of urethane), Vol.I, J.M.Burst, ed., Applied Science Publishers, pp.1-76 (1978).Suitable polyvalent alcohol representative substances comprises polyester, polylactone, polyethers, polyolefine, polycarbonate polyol and various other polyvalent alcohol.
The illustrative example of polyester polyol is poly-(alkylidene chain docosandioic acid ester) glycol, and it uses the aliphatic diol of molar excess to prepare by conventional esterification process with respect to chain docosandioic acid (alkanedioic acid).The illustrative example that can be used for preparing the glycol of polyester is ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1, ammediol, 1,4-butyleneglycol and other butyleneglycol, 1,5-pentanediol and other pentanediol, hexylene glycol, decanediol and dodecanediol.The preferred aliphatic series glycol comprises 2 to 8 carbon atoms.The illustrative example that can be used for preparing the diprotic acid of polyester is toxilic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, 2-methyl isophthalic acid, 6-caproic acid, pimelic acid, suberic acid and dodecanedioic acid.The preference chain docosandioic acid comprises 4 to 12 carbon atoms.The illustrative example of polyester polyol is poly-(hexylene glycol adipic acid ester (adipate)), poly-(butyleneglycol adipic acid ester), poly-(glycol adipate), poly-(glycol ether adipic acid ester), poly-(hexylene glycol barkite (oxalate)) and poly-(ethylene glycol sebate (sebecate)).
Being used for poly-lactone polyol of the invention process is two or three or tetratomic in essence.Such polyvalent alcohol by internal ester monomer with have the initiator for reaction preparation that contains active hydrogen group, the illustrative example of internal ester monomer is δ-Wu Neizhi, 6-caprolactone and ε-methyl-6-caprolactone, ξ-enanthol lactone (enantholactone), illustrative example with the initiator that contains active hydrogen group is ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol and TriMethylolPropane(TMP).The production of polyvalent alcohol is known in the art like this, for example referring to United States Patent(USP) Nos. 3,169, and 945,3,248,417,3,021,309 to 3,021,317.Ester polyol is two, three and the tetrahydroxy official energy 6-caprolactone polyvalent alcohol that is called polycaprolactone polyol in preferred.
Polyether glycol comprises those that are obtained by the oxyalkylation of suitable beginning molecule and alkylene oxide, wherein alkylene oxide such as ethene, propylene, butene oxide or its mixture.The example of initiator molecule comprises that water, ammonia, aniline or polyvalent alcohol such as molecular weight are 62 to 399 dibasic alcohol, especially alkane polyol such as ethylene glycol, propylene glycol, hexamethylene glycol, glycerine, TriMethylolPropane(TMP) or trimethylolethane or comprise low-molecular-weight alcohol such as glycol ether, triglycol, dipropylene glycol or the tripropylene glycol of ether group.Other normally used initiator comprises tetramethylolmethane, Xylitol, arabitol and sorbyl alcohol, mannitol.For producing elastomerics, use poly-(propylene oxide) polyvalent alcohol that comprises poly-(propylene oxide-ethylene oxide) polyvalent alcohol.Preferred ethylene oxide content should come from different backgrounds and possess different abilities pure gross weight less than 40 weight % with preferably less than 25 weight %.Can adopt any way to introduce oxyethane along polymer chain, in other words the meaning is that the representative ring oxidative ethane can be introduced as the end block in inner block, can be along the polymer chain random distribution, or random distribution in ethylene oxide-propylene oxide block endways.These polyvalent alcohols are the conventional materials by the ordinary method preparation.
Other polyether glycol comprises poly-(tetrahydrofuran (THF)) polyvalent alcohol that is also referred to as poly-(oxygen tetramethylene) glycol, and it is commercial to be dibasic alcohol.These polyvalent alcohols stop and prepare from the positively charged ion open loop of tetrahydrofuran (THF) and by water, as at Dreyfuss, and P. and M.P.Dreyfuss, Adv.Chem.Series is described in 91,335 (1969).
The polycarbonate that comprises hydroxyl comprise self known those, the product that obtains from the reaction of following material for example: dibasic alcohol such as propylene glycol-(1,3), butyleneglycol-(1,4) and/or hexylene glycol-(1,6), glycol ether, triglycol or four ethylidene glycols and diaryl carbonate, for example diphenyl carbonate or phosgene.
The illustrative example that is applicable to various other polyvalent alcohols of the present invention is alkoxylate adducts, vinylchlorid/vinyl acetate/vinyl alcohol copolymer, vinylchlorid/ethylene acetate/acrylic acid hydroxypropyl acrylate multipolymer, the vinylformic acid 2-hydroxyl ethyl ester of vinylbenzene/allyl alcohol copolymer, dihydroxymethyl Dicyclopentadiene (DCPD), the multipolymer of ethyl propenoate and/or butyl acrylate or 2-EHA, Propylene glycol monoacrylate, the multipolymer of ethyl propenoate and/or butyl acrylate or 2-EHA.
Operable other polyvalent alcohol is included in that to contain at least two hydroxyls and number-average molecular weight in the molecule be 1,000 to 5,000 hydrogenated polyisoprene or polyhutadiene.Also can use as being described in the non-hydrogenation polybutadiene polyol of U.S. patent 5,865,001.
In order to be used for the present invention, the number-average molecular weight of hydroxy-end capped polyvalent alcohol is 200 to 10,000 generally speaking.The molecular weight of preferred polyol is 300 to 7,500.More preferably the number-average molecular weight of polyvalent alcohol is 400 to 6,000.According to the initiator of producing polyvalent alcohol, the functionality of polyvalent alcohol is 1.5 to 8.The functionality of preferred polyol is 2 to 4.Produce elastomerics for dispersion according to the present invention, preferably use the blend of polyvalent alcohol or polyvalent alcohol to make the nominal functionality of polyvalent alcohol or blend be equal to or less than 3.
It is two or more to can be used for being characterized as of chainextender of the present invention, preferred two functional groups, and each functional group comprises " active hydrogen atom." form of these functional groups be preferably hydroxyl, primary amino, secondary amino group, and composition thereof.Term " active hydrogen atom " is expressed as follows hydrogen atom: this hydrogen atom according to Kohler at J.Am.Chemical Soc., 49, Zerewitinoff described in the 31-81 (1927) test, it is the position display activity in molecule.Chainextender can be aliphatic, alicyclic or aromatics, is illustrated as dibasic alcohol, trivalent alcohol, tetravalent alcohol, diamine, tertiary amine and amino alcohol.The illustrative example of two functional chain extenders is an ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1,5-pentanediol and other pentanediol, 1,6-hexylene glycol and other hexylene glycol, decanediol, dodecanediol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 1, the 4-cyclohexanediol, 1, two (2-hydroxyl-oxethyl) hexanaphthenes of 4-, 1, two (2-hydroxyl-oxethyl) benzene of 4-, esterdiol 204, the N-Mono Methyl Ethanol Amine, N-methyl isopropyl amine, the 4-Trans-4-Amino Cyclohexanol, 1 (diaminotheane), 1, the 3-diaminopropanes, diethylenetriamine, Toluene-2,4-diisocyanate, the 4-diamines, and toluene-1, the 6-diamines.The aliphatic cpd that preferably comprise 2 to 8 carbon atoms.If preparation thermoplasticity or solubility urethane, chainextender is two functional in itself.The illustrative example of useful amine chainextender is quadrol, single carbinolamine and propylene diamine.If preparation thermoset or insoluble urethane, chainextender can be two senses or higher polyfunctional in itself.The illustrative example of higher functional chain extenders, they use with the small number of total chainextender 1 to 20 weight % usually, are glycerine, 1,1,1-hydroxymethyl ethane, 1,1,1-TriMethylolPropane(TMP), tetramethylolmethane and 1,3,6-hexanetriol.
Since aqueous phase they with the rapid reaction of isocyanic ester, preferably chainextender is a polyhydric alcohol amine.Special preferred chain extenders is selected from the amine terminated polyether, for example available from JEFFAMINE D-400, aminoethylpiperazine, the 2-methylpiperazine, 1 of Huntsman ChemicalCompany, 5-diamino-3-methyl-pentane, isophorone diamine, two (amino methyl) hexanaphthene and isomer thereof, quadrol, diethylenetriamine, amino ethyl ethanolamine, Triethylenetetramine (TETA), triethylene five amine, thanomin, with its Methionin and salt, hexanediamine, hydrazine and the piperazine of any stereoisomer form.
Other chainextender comprises phenylenediamine or methylene diamine (MDA), uncle or secondary diamine.These materials can be generally by
R
1HN-Ar-NHR
1And R
1HN-Ar-CH
2-Ar-NHR
1
Expression, wherein Ar represents aromatic ring and each R
1Be the alkyl that comprises 1 to 20 carbon atom independently.Preferred alkyl comprises 1 to 10 carbon atom.More preferably alkyl comprises 4 to 8 carbon atoms.The commercially available prod comprises the UNILINK available from UOP
TMDiamines.Other useful chainextender comprises the halogen or the alkyl-substituted derivative of following material: (blocked) MDA or the phenylenediamine of methylene-dianiline or phenylenediamine and sealing.Example comprises that methylene-bis (Ortho-Chloro aniline) (MOCA) and methylene-bis (two-tertiary butyl aniline).The example of the amine of sealing comprises the CAYTUR that purchases Uniroyal
TMThe end-blocking solidifying agent.
Polyurethane composition of the present invention comprises 2 to 25 weight %, preferred 3 to 20 weight %, more preferably 4 to 18 weight % chain extender component.
As required, optionally a small amount of monohydroxy or mono amino functional compound are commonly referred to " chain terminator ", can be used for controlling molecular weight.The illustrative example of chain terminator is propyl alcohol, butanols, amylalcohol and hexanol like this.When using, chain terminator uses with following small number: the 0.1 weight % of entire reaction mixture that obtains polyurethane composition is to 2 weight %.
Polyurethane preparation those skilled in the art are well known that if all difunctional's compounds, and promptly two sense polyvalent alcohols, two functional isocyanate and two functional chain extenders are used to prepare this urethane, can obtain thermoplasticity or solvability and mouldable urethane.Polyurethane preparation those skilled in the art also are well known that if functionality adopts or is used in combination with two sense polyvalent alcohols, isocyanic ester or chainextender greater than two any or multiple polyvalent alcohol, isocyanic ester and chainextender are independent, obtain thermoset or insoluble and obstinate urethane.
Polyurethane prepolymer compositions of the present invention comprises the unreacted NCO of 1 to 20 weight %, preferred 2 to 15 weight %NCO, more preferably 2 to 10 weight %NCO.
The feature of polyurethane composition of the present invention can be subjected to comprising that polyvalent alcohol adds the overall mol ratio influence of the mixture of chainextender to two (isocyanatomethyl) compounds significance degree, and so generally speaking ratio is 0.95 to 1.1.This mol ratio of reactant is for all actual purpose, can obtain essentially identical result to the ratio of isocyanurate equivalent or isocyanate groups by isocyanate-reactive equivalent or hydroxyl in the reference reaction mixture.The inverse of these ratios, promptly isocyanurate equivalent is called " isocyanate index " to the normal ratio of active hydrogen part.
Optionally, a small amount of one or more polyfunctional isocyanates except that two (isocyanatomethyl) cyclohexane isomer can be used for reaction mixture.The illustrative example of isocyanic ester is 2 like this, 4-and 2,6-tolylene diisocyanate, 4.4 ' phenylene vulcabond, 4,4 '-diphenylmethanediisocyanate, and to phenylene vulcabond, 1,5-naphthalene diisocyanate, 1, hexamethylene-diisocyanate, two (2-isocyanate group (isocyanato)) fumarate, 4,4 '-bicyclohexane methyl vulcabond, 1,5-tetrahydrochysene naphthalene diisocyanate, isophorone diisocyanate and 4,4 '-methylene-bis (cyclohexyl) isocyanic ester.A small amount of other polyfunctional isocyanate can for total polyfunctional isocyanate of being used for preparaton 0.1% to 20% or more, preferred 0% to 10%.
Optionally, the catalyzer of improvement or the formation of promotion urethane group can be used for preparaton.The illustrative example of useful catalyzer is stannous octoate, dibutyl tin laurate, stannous oleate, metatitanic acid tetrabutyl tin, tributyltin chloride, cobalt naphthenate, dibutyltin oxide, potassium oxide, tin chloride, N, N, N, N '-tetramethyl--1,3-butanediamine, two [2-(N, the N-dimethylamino) ethyl] ether, 1,4-diazabicyclo [2.2.2] octane, zirconium chelate, aluminum chelate and bismuthyl carbonate (bismuthcarbonate) are as at Paint ﹠amp; Coatings Industry (paint ﹠amp; Coatings industry), metalcatalyzed urethane systems (the urethane system of metal catalytic), XVI, No.10 is described in the 80-94 (Oct.2000).If preparation micropore product advantageously adopts the catalyzer of the binding substances of tertiary amine compound and organo-tin compound as the reactant preparaton.When using, catalyzer uses with catalytic quantity, and this catalytic quantity scope can be 0.001% and lower to 2% and Geng Gao, in the total quantity of the composition of formation urethane.
But the feature thermoplasticity of polyurethane composition of the present invention or heat cured, and these materials can be according to different process preparations.When total mol ratio of reactant is that the summation that two sense polyvalent alcohols add two functional chain extenders is for the moment to two (isocyanatomethyl) compounds substantially, can prepare thermoplastic polyurethane composite of the present invention.The form of that is to say is that to have and/or do not have amino hydroxyl or other gross activity hydrogen equivalent that contains active hydrogen group be one to the ratio of isocyanate group (isocyanato) equivalent overall number substantially.The reaction of preparation urethane of the present invention can be carried out in body or in suitable solvent, and the illustrative example of solvent is dimethyl formamide and pimelinketone, generally carries out several minutes to several hours time under 70 ℃ to 160 ℃ high temperature.After guaranteeing to react the analysis of all isocyanate groups effectively, urethane can be cooled off, stripping and slicing becomes powder, and dry, if prepare in solvent, stores and is processed into useful article then.Can add non-essential composition such as catalyzer, tinting material etc.As required, polyurethane solution can be spun into elastomeric fibre by wet spinning process as the technology that is used to prepare spandex.
The whole bag of tricks can be used for preparing thermoplastic polyurethane of the present invention.So-called " single step " method is arranged in these methods, wherein will comprise polyvalent alcohol, organic diisocyanate, if chainextender and other mixture of ingredients that exists are at high temperature mixed simultaneously and are reacted, for example simply at J.Applied Polymer Sci., described in 19,2491 (1975).Preferably, mix two sense polyvalent alcohols and two functional chain extenders.Then this mixture and two (isocyanatomethyl) compounds are heated to 70 ℃ to 165 ℃ respectively.Then polyvalent alcohol/mixture of chain extenders is being joined in two (isocyanatomethyl) compounds under the agitation condition fast.Perhaps, can adopt quick stirring that the isocyanic ester of heating is joined in polyvalent alcohol/mixture of chain extenders.After thorough mixing, reaction mixture is reacted under suitable heating condition, so remaining on 70 ℃ to 165 ℃, temperature begins to solidify up to viscous mixt, this continues two minutes to ten minutes or longer time usually.Reaction object piece (mass) is partly solidified product now, this product can be taken out and dwindle into stripping and slicing or pelletized form easily.Product can thermoplasticity processing and be applicable to by various technology such as compression molding, extrude and injection moulding manufactures finished article, as urethane make those skilled in the art known.
The another kind of typical method of preparation thermoplastic polyurethane of the present invention comprises so-called " prepolymer " method, wherein two (isocyanatomethyl) compounds reactions of polyvalent alcohol and sufficient amount, to obtain isocyanate-terminated prepolymer, its illustrative example is the average structure that structural formula V shows:
Isocyanate-terminated prepolymer
Structural formula V
Then isocyanate-terminated prepolymer and two functional chain extenders are reacted under the temperature and time that is used for " single step " thermoplastic polyurethane, reclaim storage and be used for later purposes.Prepolymer can use immediately or it can store be used for after with chainextender reaction.Can adopt the various schemes of this prepolymer technology, the illustrative example of these schemes be with two functional chain extenders at first with di-isocyanate reaction to form prepolymer, then subsequently with polyol reaction.The formation of hydroxyl-terminated prepolymer can be by one mole of two (isocyanatomethyl) compounds of reaction and two moles of polyvalent alcohols, with two moles and chainextender blended polyvalent alcohol, or with the reaction of two moles of chainextenders, the remaining isocyanic ester of reaction and any polyvalent alcohol or chainextender in subsequent reaction then.
When the overall proportion of reactant is a summation that polyvalent alcohol adds chainextender when two (isocyanatomethyl) compounds is 1.0 to 1.1, but can prepare the thermoplasticity millable gums.But millable gums can be by " single step " technology or " prepolymer " prepared, and wherein under 50 ℃ to 165 ℃ temperature, the reaction times can arrive several hours for several minutes.The urethane that obtains can be able to be milled product or glue and other two (isocyanatomethyl) compounds or other multifunctional polyisocyanates thorough mixing on rubber mixing mill solidify under heat and suitable pressure in mould then.Other polyisocyanates reacts with the active hydrogen atom of any remnants that exist with hydroxyl and/or amine-format.If think by with the H-H reaction of urethane group and/or the urea groups that exists, this reaction causes branching and crosslinked therefore to form allophanate and/or biuret linkage.But millable gums also can adopt peroxide cure, and the illustrative example of superoxide is dicumyl peroxide and benzoyl peroxide.In the case, extract hydrogen atom to form free radical from polyvalent alcohol or chainextender.Stable crosslinked from the combined with radical of various chains to form.If introduce unsaturated part, can adopt sulphur cross-linked rubber in vulcanization reaction by polyvalent alcohol or chainextender.
She Xiang another kind of useful type polyurethane product is that density is 15 to 60 in the present invention, preferred 20 to 55 pounds every cubic feet micro-pore elastomer polyurethane product and foam.Microvoid polyurethane is the high-density with the whole cortex of desired thickness, 15 to 60 pounds/cubic feet, and closed pore, high performance polyurethane foam.Such micropore product is thought the important commercial engineering materials, and this material has non-porous elastomeric desired properties, but because their less dense, the cost of each molded article is lower.Microvoid polyurethane is used for bumper and dashboard, heel, industrial tire, industrial roll and many other industrial application.
Prepare microvoid polyurethane product of the present invention by two kinds of reactive fluid logistics of processing in urethane metering-hybrid machine.A kind of liquid stream comprises two (isocyanatomethyl) compounds and optionally whipping agent such as halocarbon or similar volatility, nonreactive compound.If the water that other liquid stream comprises polyvalent alcohol, chainextender, catalyzer usually and uses.Usually the active hydrogen atom equivalent is about one to the normal ratio of two (isocyanatomethyl) compounds, and promptly for each isocyanurate equivalent, the gross activity hydrogen equivalent is 0.95 to 1.05.Whipping agent is such compound, and this compound is inert and does not disturb urethane reaction technology nocuously and can or be lower than the volatilization of this temperature of reaction under the temperature of reaction that relates to and cause that gelationization reaction object piece becomes foam.Required whipping agent is water, halohydrocarbon and low boiling hydrocarbon, and their illustrative example is the single fluoromethane of trichlorine, methylene dichloride, trichloromethane, dichloro list fluoromethane, methyl chloride, 1,1-two chloro-1-fluoroethanes, 1,1,2-three chloro-1,2,2-Halothane, 1,1,1,2-Tetrafluoroethane (HFC 134a), 1,1,1,3,3,-3-pentafluorobutane (365mfc), 1,1,1,3,3-pentafluoropropane (245fa) and pentane, (Skellysolve A, iso-pentane and pentamethylene) hexane.
The method for preparing microvoid polyurethane comprises that the liquid mixture of carrying pre-determined quantity enters heating, but closing molding.The logistics that will contain isocyanate group remains under 25 ℃ to 90 ℃ the temperature usually, and the logistics that will contain polyvalent alcohol remains under the temperature that remains on 30 ℃ to 100 ℃ under 30 ℃ to 100 ℃ the temperature and with mould usually.Closing molding, reactive component begin reaction and produce heat.Heat causes that whipping agent volatilization and reaction mixture bubble.Simultaneously, reaction mixture gels is solidified into the closed-cell foam that forms whole cortex at die surface then.Because die surface is colder than bulk reaction mixture, so form cortex.In the related process of also imagining in the present invention, in the technology that is called " reaction injection molding(RIM) " or RIM technology, finish mixing by the static mixer of the closed mold inlet that is placed on heating.
In preparing the method for microcellular polyurethane elastomer, need usually to use to count low quantity of surfactant or the emulsifying agent of 0.001 weight % to 2.0 weight % with total reaction mixture.The illustrative example of tensio-active agent is the polyoxyalkylene adducts of polysiloxane-polyxyalkyl-blockpolymer, alcohol, wherein oxyethane be added to that alcohol is gone up, dimethyl silicone oil and polyethoxylated vegetables oil.
Optionally, the known various properties-correcting agent of urethane manufacturing those skilled in the art can join in the preparaton that forms polyurethane elastomer.The illustrative example of these reagent is carbon black, titanium dioxide, zinc oxide, various clay, various pigment, filler, dyestuff and other tinting material, does not comprise the softening agent of any reactive terminal group, lacks and cut glass, carbon, graphite and special fibre, releasing agent and stearic acid material.
Urethane of the present invention is used as heel, pad, solid tyre, fascia and collision bumper, toy, furniture, utensil and business machine housings, animal rearing groove, printing roller, toy, tackiness agent, coating, sealing agent, fiber, is used as powder, optical lens, protective shield, wheel and many other commercial uses of powder coating.
Below provide some embodiment to further specify the present invention.Should understand unless otherwise indicated, all operating under the nitrogen atmosphere carried out.All equally, unless otherwise indicated embodiment carry out at ambient temperature.
Composition and the test that is used for embodiment described in following terminology:
Terminology
Catalyzer 1-with Dabco
TMT-12 is available from the dibutyl tin laurate of Air Products Company.
Chainextender 1-1, the 4-butyleneglycol.
Isocyanic ester 1-1, two (isocyanatomethyl) hexanaphthenes and 1 of 3-, 50/50 mixture of two (isocyanatomethyl) cyclohexane isomer of 4-.
Isocyanic ester 2-available from 1 of Aldrich Chemical Company, two (isocyanatomethyl) cyclohexane isomer of 4-, 50/50 cis/trans ratios.
Isocyanic ester 3-4,4 '-methylene-bis (cyclohexyl isocyanate) or 4,4 '-dicyclohexyl methane diisocyanate, with Desmodur
TMW is available from Bayer AG.This isocyanic ester is also referred to as H
12MDI.
Polyvalent alcohol 1-number-average molecular weight is approximately poly-(oxygen tetramethylene) glycol of 2,000.
Polyvalent alcohol 2-number-average molecular weight is approximately 1000 polycaprolactone glycol, with Tone0240 available from The Dow Chemical Company.
Compression set, method B; ASTM D 395, the test method of rubber performance-compression set.When testing under load, numerical value is high more, and elastomerics is easy to continuous deformation more.
Second-order transition temperature, the resilience of Tg-dsc-elastomerics is transformed into the temperature of rubber-like material from glassy material under it.
Resilience, the Bashore resilience; ASTM D 430, rubber deterioration, the test method of dynamic fatigue.Numerical value is high more, and the elastomerics resilience is big more.
Shore hardness; ASTM D 2240, the test method of rubber performance-durometer hardness.Numerical value is high more, and elastomerics is hard more.
Softening temperature-thermo-mechanical analysis.Elastomerics begins the remollescent temperature under it.
Stress-strain property--fracture tensile strength, elongation limit, 100% and 300% modulus (stress under 100% and 300% elongation); ASTM D412, the test method of rubber performance in the tension force.
Tear strength; Graves die head C, ASTM D 624, the test method of rubber performance-tear strength.Numerical value is high more, and elastomerics is got over anti tear.
Embodiment 1
The mixture of 3-cyano group-1-hexanaphthene formaldehyde (cyclohexanecarboxaldehyde) and 4-cyano group-1-hexanaphthene aldehyde products (cis of every kind of isomer and trans forms) is from the process preparation of 3-tetrahydrobenzene-1-nitrile according to U.S. patent 6,252,121.
Dropping 4.25 restrains aldehyde mixtures and the mixture that obtains was at room temperature stirred 4 hours in the ammonia soln in ice bath (28 weight %, 31 milliliters).White solid is leached, dry in a vacuum 2 hours, be dissolved in methyl alcohol (30 milliliters) and hydrogenation 3 hours in the presence of nickel on the silica/alumina (0.2 gram) and ammonia (6 restrain) under 950psi and 100 ℃.Product comprises 1,3-and 1, two (isocyanatomethyl) hexanaphthenes of 4-.The product yield that is recorded by gas-chromatography is 93%.The vacuum distilling of thick diamines (4 gram) obtains 2.57 grams ebullient pure material under 73 ℃/1mmHg,
13CNMR (CDCl
3, ppm): 20.28; 25.15; 25.95; 28.93; 29.84; 30.30; 32.04; 34.48; 35.74; 38.61; 40.53; 41.02; 45.45; 45.91; 48.30; 48.47.By phosgenation, diamine changes into 1,3-, 1, two (isocyanatomethyl) hexanaphthenes (W.Siefken, Ann.Chem., 562,75 (1949)) of 4-.
Embodiment 2 and 3 and the comparative example A
Use identical polyvalent alcohol and chainextender, prepare the thermoplastic polyurethane composite of embodiment 2 and 3 and comparative example A's thermoplastic polyurethane in the following way.Polyvalent alcohol, chainextender and catalyst junction merging are preheating to 100 ℃, are weighed in 250 milliliters of plastic cups, adopt high-speed mixer to mix, several minutes outgases under vacuum.Then the polyfunctional isocyanate is joined in polyvalent alcohol, chainextender and the mixture of catalysts, with the binding substances additionally mixed several minutes of all the components.The baking oven of mixture being put into 100 ℃ is up to the beginning of observing gelationization.Gelationization is obvious after two to three minutes.Then reaction mixture is taken out the also mould of impouring teflon (teflon) coating from baking oven, this mould has been preheating to 115 ℃.Mould is put into the Carver squeezer, then 20,000psi lower compression molding one hour.The thermoplastic polyurethane sheet material that obtains was taken out 105 ℃ of baking ovens after fixing 16 hours from mould.Then sheet material is taken out from baking oven, cool to room temperature is also stored under envrionment conditions up to its physicals of test.In following Table A, provide the quantity of composition, condition of cure, and physicals.
Isocyanate index is identical with the comparative example A with 3 for embodiment 2, and it causes in embodiment 2 and 3 elastomericss 34% hard segment concentration and 33% hard segment concentration in comparative example A's elastomerics.The elastomerics of embodiment 3 has transly 1, and the maximum concentration of 4-isomer shows the highest Shore A hardness.
Table A
| Embodiment 2 | Embodiment 3 | The comparative example A | |
| Isocyanic ester 1 | Isocyanic ester 2 | Isocyanic ester 3 | |
| Preparaton (pbw) | |||
| Polyvalent alcohol 1 | ????100.00 | ????100.00 | ????100.00 |
| Chainextender 1 | ????13.05 | ????13.06 | ????8.68 |
| Isocyanic ester | ????39.42 | ????39.46 | ????39.88 |
| Catalyzer 1, weight % | ????0.072 | ????0.071 | ????0.013 |
| Isocyanate index | ????1.05 | ????1.05 | ????1.05 |
| Hard segment concentration, % | ????34 | ????34 | ????33 |
| Performance | |||
| Hardness, Shore A | ????61 | ????82 | ????73 |
| Tensile strength, psi | ????3108 | ????5031 | ????3005 |
| Elongation at break, % | ????1280 | ????893 | ????1260 |
| 100% strained stress, psi | ????220 | ????594 | ????269 |
| 300% strained stress, psi | ????286 | ????1029 | ????409 |
| Tear strength, pound/in | ????278 | ????402 | ????423 |
| Resilience | ????46 | ????54 | ????40 |
| Compression set under 70 ℃, % | ????12 | ????17 | ????24 |
| Tg (measuring) by DSC, ℃ | ????-71 | ????-69 | ????-65 |
| Softening temperature, ℃ | ????193 | ????191 | ????146 |
The further feature of the elastomerics of embodiment 2 can be powerful and tough and tensile (combination of intensity and extensibility), anti tear and resilience and unusual good compression set, good low-temperature resistance (Tg), and high-melting-point.The most of performances of embodiment 3 and comparative example A's elastomerics equate, but embodiment 3 has more rebound resilience than Comparative Examples A, is not easy to set under compression, and has higher melt temperature.
Embodiment 2,3 and comparative example A's elastomerics all is colourless and transparent.
Embodiment 4-7 and Comparative Examples B-D
For as described in the embodiment 2-3, use polyvalent alcohol 2 and the thermoplastic polyurethane composite (from isocyanic ester 1) of chainextender 1 preparation embodiment 4-7 and the thermoplastic polyurethane composite (from isocyanic ester 3) of Comparative Examples B-D as above.Hard segment concentration (weight %) is 22 to 50 for embodiment 4-7 and is 30 to 50 for Comparative Examples B-D, to allow to carry out the meaningful comparison of polyurethane elastomer physicals.Polyurethane elastomer of the present invention (embodiment 4-7) has the well balanced of mechanical property, as observed for Comparative Examples B-D.Elastomerics of the present invention has excellent performance performance (higher hardness, higher tear strength, better rebound performance and lower compression set) with respect to Comparative Examples B-D in the hard segment concentration scope.
Table B
| Title | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Preparaton (pbw) | ||||
| Polyvalent alcohol 2 | ????100.00 | ????100.00 | ????100.00 | ????100.00 |
| Chainextender 1 | ????5.69 | ????10.27 | ????17.73 | ????28.13 |
| Isocyanic ester 1 | ????22.47 | ????32.51 | ????48.92 | ????71.79 |
| Catalyzer 1 (polyvalent alcohol 2﹠1, the weight % of 4-BD) | ????0.033 | ????0.050 | ????0.050 | ????0.050 |
| Isocyanate index | ????102 | ????102 | ????102 | ????102 |
| Hard segment % | ????22 | ????30 | ????40 | ????50 |
| Performance | ||||
| Hardness, Shore A | ????65 | ????73 | ????86 | ????92 |
| Tensile strength, psi | ????4745 | ????6235 | ????6472 | ????5576 |
| 100% modulus, psi | ????248 | ????407 | ????458 | ????602 |
| 300% modulus, psi | ????377 | ????671 | ????968 | ????1266 |
| Elongation at break, % | ????1038 | ????939 | ????896 | ????679 |
| Young modulus, psi | ????666 | ????746 | ????726 | ????931 |
| Tear strength, Graves, die head C, pli | ????287 | ????416 | ????483.9 | ????530.6 |
| The Bashore resilience, % | ????43 | ????42 | ????35 | ????27 |
| Compression set, % (method B) | ????53 | ????37 | ????41 | ????58 |
| Outward appearance | Transparent | Transparent | Transparent | Limpid |
Table C
| Title | Comparative Examples B | Comparative Examples C | Comparative Examples D |
| Preparaton (pbw) | |||
| Polyvalent alcohol 2 | ????100.00 | ????100.00 | ????100.00 |
| Chainextender 1 | ????7.34 | ????13.29 | ????21.60 |
| Isocyanic ester 3 | ????35.50 | ????53.35 | ????78.20 |
| Catalyzer 1 (polyvalent alcohol 2﹠1, the weight % of 4-BD) | ????0.033 | ????0.033 | ????0.033 |
| Isocyanate index | ????102 | ????102 | ????102 |
| Hard segment % | ????30 | ????40 | ????50 |
| Performance | |||
| Hardness, Shore A | ????60 | ????83 | ????84 |
| Tensile strength, psi | ????6966 | ????8306 | ????7872 |
| 100% modulus, psi | ????350 | ????504 | ????1063 |
| 300% modulus, psi | ????638 | ????1018 | ????2297 |
| Elongation at break, % | ????1040 | ????870 | ????638 |
| Young modulus, psi | ????1727 | ????2396 | ????2519 |
| Tear strength, Graves, die head C, pli | ????327 | ????399 | ????497 |
| The Bashore resilience, % | ????35 | ????26 | ????25 |
| Compression set, % (method B) | ????72 | ????55 | ????72 |
| Outward appearance | Muddy | Transparent | Limpid |
According to the consideration or the invention process disclosed herein of specification sheets, other embodiment of the present invention is obvious to those skilled in the art.Think that specification sheets and embodiment provide as an example, true scope of the present invention and spirit are indicated by claim.
Claims (11)
1. urethane, it comprises alicyclic diisocyanate, the reaction product of polyvalent alcohol and chainextender, wherein this alicyclic diisocyanate comprises (i) anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or (ii) two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, condition is that this isomer mixture comprises at least 5 these anti-form-1s of weight %, 4 pairs of (isocyanatomethyl) hexanaphthenes.
2. isocyanate-terminated prepolymer, it is by making polyvalent alcohol and two (isocyanatomethyl) compounds prepared in reaction, wherein two (isocyanatomethyl) hexanaphthenes comprise (i) anti-form-1, two (isocyanatomethyl) hexanaphthenes of 4-or (ii) two or more cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, condition is that this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.
3. composition, it comprises cis-1, two (isocyanatomethyl) hexanaphthenes of 3-, anti-form-1, two (isocyanatomethyl) hexanaphthenes of 3-, cis-1, two (isocyanatomethyl) hexanaphthenes of 4-and anti-form-1, the isomer mixture of two (isocyanatomethyl) hexanaphthenes of 4-, wherein this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (isocyanatomethyl) hexanaphthenes of 4-.
4. composition, it comprises cis-1, two (amino methyl) hexanaphthenes of 3-, anti-form-1,3-hexanaphthene-two (amino methyl), cis-1, two (amino methyl) hexanaphthenes of 4-, and anti-form-1, the isomer mixture of two (amino methyl) hexanaphthenes of 4-, wherein this isomer mixture comprises at least 5 these anti-form-1s of weight %, two (amino methyl) hexanaphthenes of 4-.
5. urethane according to claim 1, wherein this polyvalent alcohol is poly-(tetrahydrofuran (THF)) glycol, poly-lactone polyol, poly-(ε caprolactone) polyvalent alcohol, polyester polyol, alkylene oxide polyol, poly-(propylene oxide) polyvalent alcohol, poly-(divinyl) polyvalent alcohol or ethylene oxide-capped poly-(propylene oxide) polyvalent alcohol.
6. urethane according to claim 1, wherein chainextender comprises the aliphatic diol that contains 2 to 8 carbon atoms.
7. urethane according to claim 7, wherein this aliphatic diol is 1, the 4-butyleneglycol.
8. urethane according to claim 1, wherein chainextender comprises diamine.
9. wherein except that the isomer of two (isocyanatomethyl) hexanaphthenes, also there are one or more other polyfunctional isocyanates of 0.1 to 20 weight % in polyurethane prepolymer compositions according to claim 2 in composition.
10. polyurethane prepolymer compositions according to claim 9, wherein other polyfunctional isocyanate comprises methyldiphenyl group diisocyanate, isophorone diisocyanate, tolylene diisocyanate, HDI or H12MDI (hydrogenation MDI).
11. urethane according to claim 1, its form is drip molding, mo(u)lded item, curtain coating part, be spun into goods, reaction injection molding(RIM) part, blowing part, moulding or extrusion molding spare.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/284,993 US20040087754A1 (en) | 2002-10-31 | 2002-10-31 | Polyurethane compounds and articles prepared therefrom |
| US10/284,993 | 2002-10-31 |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200422314A (en) | 2004-11-01 |
| AU2003279938A1 (en) | 2004-06-07 |
| CN1328298C (en) | 2007-07-25 |
| EP1560865A1 (en) | 2005-08-10 |
| US20040087754A1 (en) | 2004-05-06 |
| MXPA05004673A (en) | 2005-06-08 |
| CA2504166A1 (en) | 2004-05-21 |
| JP2006504843A (en) | 2006-02-09 |
| WO2004041899A1 (en) | 2004-05-21 |
| BR0315066A (en) | 2005-08-16 |
| KR20050065658A (en) | 2005-06-29 |
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